Process for preparing a methano-polycyclic hydroquinone

ABSTRACT

A PROCESS FOR PREPARING A METHANO-POLYCYCLIC HYDROQUINONE WHICH COMPRISES REARRANGING A CORRESPONDING METHANO-POLYCYCLIC QUINONE UNDER ISOMERIZATION CONDITIONS IN THE PRESENCE OF AN INERT SOLVENT AND WATER AND THEREAFTER RECOVERING THE DESIRED HYDROQUINONE PRODUCT.

United States Patent r 3,810,945 PROCESS FOR PREPARING A METHANO POLYCYCLIC HYDROQUINONE Arthur W. Carlson, Crystal Lake, 111., assignor to Velsicol Chemical Corporation, Chicago, 11].

No Drawing Original application 1969 l l' versions of the quinone to the desired hydroquinone and 714,023. Divided and this application Feb. 15, 1972, Ser. No. 226,507

Int. Cl. C07c 39/24 US. Cl. 260619 F 10 Claims ABSTRACT OF THE DISCLOSURE Patented May 14, 1974 t 2 quinone to its corresponding hydroquinone in the presence of, water and an inert solvent under isomerization conditions. Utilization of this procedure avoids the necessity ofan added catalytic material for the rearrangement with its associated disadvantages. Moreover, employment of water to effect therearrangement achieves high conpermits the hydroquinone product to be readily recovered in a highly pure state free of catalyst contamination.

The rearrangement of a methano-polycyclic quinone to its corresponding hydroquinone can be represented by methane-polycyclic quinone under isomerization condi- U tions in the presence of an inert solvent and water and thereafter recovering the desired hydroquinone product.

Methano-polycyclic hydroquinones, such as 5,6,7,8,9,9- I

hexachloro-5,8-methano-5,8-dihydro-1,4 naphthohydroquinone, are valuable industrial chemicals having a variety of diiferent applications, such as insecticides or flame retardants for polymer systems, for example polyesters.

These hydroquinones are also valuable as intermediates I in the preparation of other valuable compounds, such as 2,3-epoxy propoxy derivatives obtained by reacting the hydroquinone with an epihalohydrin. These hydroquinones are usualy prepared by first forming a corresponding methano polycyclic quinone by reacting a quinone or a naphthoquinone with a cyclic diolefin, such as a cyclopentadiene under Diels-Alder conditions. The quinone adduct thus formed is then converted or rearranged to the desired hydroquinone under isomerization conditions in the presence of a solvent and a catalyst, such as a basic material, for example, pyridine or sodium hydroxide, or an acidic material, for example, sulphuric acid. This rearrangement step of the preparation is not particularly satisfactory, however, and suffers from a number of disadvantages. The presence of a catalytic material frequently adversely affects the hydroquinone product. For example, the employment of'a basic catalyst such as'caustic causes a significant development of initial color requiring, a decolorizing carbon to give a color free product andthe use of an acidic catalyst such as p-toluene sulfonic' acid causes a later development of color rendering the product commercially undesirable. Moreover, extensive purification of the hydroquinone product is usually required, especially When it is to be further reacted, because the catalytic materials have a high afiinity for the quinone product and are not readily removed by simple purification techniques.

An object of this invention, therefore, is to provide an improved process for preparing methano-polycyclichy: droquinones utilizing the rearrangement of corresponding methano-polycyclic quinones. Another object is to avoid the employment of basic or acidic catalytic materials for the rearrangement. A further object is to eifect the rearrangement with the obtainrnent of high conversion of;

the quinone to the desired hydroquinone and,rno reover, in a particularly desirable industrial manner. These and other objects of this invention will be apparent from the following detailed description thereof. i

The objects of this invention are realized by effecting. the rearrangement or conversion of amethano-polycyclic the following equations illustrating the rearrangement of a methanonaphthoquinone and a methanoanthroquinone, respectively:

where X is selected from the group consisting of hydro;

I The .rnethano-polycyclic quinones .of the above' formu lae I and-III represent quin'ones which" can be suitably' rearranged according to the process of this invention in the presence-ofwater. and an inert solvent while the .rnethano-polycyclic, hydroquinones .of formulae II and IV rep-- resent thehydroquinone products obtained. In general, a

wide 7 group; of differentmethanowpolycyclic quinones can* be rearranged-.10 the corresponding" hydroquinonesaFori example, in the above formulae, X can be hydrogen or: a halogen such aschlorine or bromine, and R R R R R .andR individually, can be hydrogen; a halogen? such as chlorine or bromine; aryl;.suehras phenyl or.sub-

stituted phenyl; or an aliphatic radical, such as alkyl or; alkenyl -having,-from one'to about ten carbon atoms. Typical examples of the-quinones of formulae land III include such compounds as:

" 5,8-methano-3,8-dihydro-l,4 naphthoquinone,'

5,8-methano-5,8 dihydro-2-methyl-1,4naphthoquinone,'

5,8-methano-5,8-dihydro-2,3-dially'lphthoquir1one, 5,8-methano-5,8- dihydro-2,3-dichloro-1,4-

naphthoquinone, 1 v

3. 5,8-methano-5,8-dihydro-2,3-dimethylnaphthoquinone, 5,8-methano-5,8-dihydro-2-ethyl-1,4-naphthoquinone, 5,6,7,-8-tetrachloro-5,8-methano-5,8-dihydro-1,4-

naphthoquinone, 5,6,7,8,9,9-hexachloro-5,8-methano-5,8-dihydro-1,4- naphthoquinone, 5,6,7 ,8,9,9-hexabromo-5,8-methano-5 ,8-dihydro- 1,4-

naphthoquinone, 5,6,7,8,9,9-hexachloro-5,8-methano-5,8-dihydro-2- methyl-1,4-naphthoquiuone, I 2,3,5 ,6,7 ,8,9,9-octachloro-S 8-methano-5 ,S-dihydro- 1 ,4-

naphthoquinone, 5,8-methano-5,8-dihydro-9,lo-anthroquinone, or 5,6,7,8,11,1l-hexachloro-5,8-methane-5,8-dihydro-9,l0-

anthroquinone.

Of the various methano-polycyclic quinones which can be rearranged to the corresponding hydroquinones, the quinones which are most effectively rearranged and which constitute the preferred starting material for use in the process of this invention are the polyhalogenated methanophthoquinones represented by Formula I above where X is a halogen such as chlorine. The methanopolycyclic hydroquinone products of the rearrangement represented by the Formulae II and IV above correspond to the above illustrated quinones and typical illustrated hydroquinones include:

While the methane-polycyclic quinones and hydroquinones are described herein for purposes of simplicity as quinones or hydroquinones, they can also be described by other nomenclature systems. For example, 5,8-methano-5,8-dihydro-1,4-naphthoquinone can also be described as 5,8 methano4,,,5,8,8,r-tetrahydronaphthalenedione-1, 4 and 5,8-methano-5,8-dihydro-l,4-naphthohydroquinohe can be described as 5,8-methano-1,4-dihydroxy-4 ,5,8,8,,- tetrahydronaphthalene.

The solvents which can be used with water to effect the rearrangement can include a wide variety of different materials. In general, most solvents which are inert to the quinone starting material and the hydroquinone product, capable of forming a substantially homogeneous solution of the quinone, hydroquinone and water at moderately elevated temperatures and which permits the hydroquinone to crystallize out at moderately low temperatures can be utilized. Typically, the solvent is an organic material and include such solvents as alcohols, for example, methyl alcohol, ethyl alcohol, or isopropyl alcohol; nitriles such as acetonitrile; others such as methyl or ethyl diethers; or ketones such as acetone or methyl ethyl ketone 4 as well as various combinations thereof. 0f the many solvents which can be used, alcohols and especially lower alkanols having from 1 to about 5 carbon atoms, such 'as methyl alcohol, are preferred. The quantity of the solvent employed can be varied with the optimum quantity being a function of the particular solvent or combination of solvents, the quinone undergoing rearrangement as well as the isomerization conditions of temperature and pressure employed. Typically, however, when using solvents such as methanol, the quantity employed can range from about 1 to about 15 weight parts of solvent per 1 weight part of the quinone undergoing rearrangement with from about 2.5 to about 12 weight parts of solvent per 1 weight part of the quinone usually being preferred.

The quantity of the water used in combination with the above described solvents can also be widely varied with the particular optimum quantity selected to maximize conversion to the desired hydroquinone being dependent upon similar factors such as the type and quantity of the solvent and the particular quinone undergoing rearrangement. Usually, however, the amount of water can range from about 0.10 to about 2.0 Weight parts of water per 1 weight part of the quinone with a more limited range of from about 0.20 to about 1.25 weight parts of water per 1 weight part of the quinone being preferred, especially when employing a preferred solvent such as methanol within the aforementioned ranges.

The isomerization conditions of temperature and pressure utilized to effect the rearrangement can vary and are interrelated to the solvent, its quantity and the amount of water used, as well as the particular quinone undergoing rearrangement. Usually, the temperature can range from about 25 C. to about 200 C. with a more limited range of from about 50 C. to about C. usually being preferred. An especially preferred and convenient operating temperature, however, is the refluxing temperature of the reaction mixture which will vary within the above ranges depending upon such factors as the solvent or solvent mixture, the quantity of the Water present and the pressure. While the rearrangement can be effectively conducted at the above temperature ranges at atmospheric pressures, it may be desirable in certain instances, especially to increase conversion, to operate at an elevated pressure ranging from about 1 to about 4 atmospheres above atmospheric pressure. The duration of the rearrangement or the period of time necessary to achieve the desired conversion effected under such isomerization conditions will vary but usually ranges from about 1 to about 15 hours.

After the desired degree of conversion has been achieved, the methane-polycyclic hydroquinone product can be readily recovered from the reaction mixture by simply cooling to crystallize the product which can then be readily recovered by conventional filtration techniques. This, of course, avoids the more complicated recovery procedures required when the rearrangement is effected in the presence of a catalytic material. If desired, the hydroquinone product can then be further purified to an extremely pure state according to conventional techniques such as crystallization.

The rearrangement process of this invention can be effected in either a batch or continuous type operation. A batch operation is usually preferred, however, and an illustrative procedure involves charging the appropriate quantitives of the quinone to be rearranged, for example 5,6,7,8,9,9-hexachloro-5,8-methano 5,8 dihydro 1,4- naphthoquinone, the desired solvent, such as methyl alco hol, and water to a reaction vessel. The reaction mixture is then heated, preferably to reflux temperature, and maintained thereat for a period of time necessary to effect the desired conversion. The mixture is then cooled to crystallize the product which can then be separated from the reaction mixture by filtration, washed and, if neces- EXAMPLE 1 The process of this invention was used to prepare a methano-polycyclic hydroquinone from the corresponding quinone according to the following procedure of Part A. The same procedure was used in Part B, but water was not present during the rearrangement according to this invention.

Part A 5,6,7,8,9,9-hexachloro 5,8 methano 5,8 dihydrol,4-naphthoquinone 5 grams, methyl alcohol 44 grams and water 5 grams were charged to a reaction flask equipped with an overhead reflux column. The mixture was heated to reflux (68 to 71 C.) and maintained thereat for 3 hours. The mixture was then cooled and analysis by infrared spectroscopy indicated conversion of 99 percent to the desired 5,6,7,8,9,9-hexachloro-5,8- methano-5,8-dihydro-1,4-naphthohydroquinone.

PartB Using the same general procedure of Part A, 5 grams of the same quinone and methyl alcohol, 48 grams, were heated at reflux for 3 hours. The conversion to the desired hydroquinone product was 21 percent.

EXAMPLE 2 Using the general procedure of Example 1, 5,6,7,8,9,9- hexachloro 5,8 methano-5,8-dihydro-l,4-naphthohydroquinone was prepared by heating the corresponding quinone, 5 grams, water, 5 grams, and methyl ethyl ke tone, 32.2 grams, at reflux (76 C.) for 1 hour. The conversion to the desired hydroquinone product was 90 percent.

EXAMPLE 3 Using the general procedure of Example 1, 5,6,7,8, 11,1l-hexachloro 5,8 dihydro 5,8 dimethano-9.lanthroquinone is prepared by heating at reflux 5,6,7,8, 11,11-hexachloro 5,8 dihydro 5,8 dimethano-9,10- anthroquinone grams, water 5 grams and methyl alcohol 50 grams.

EXAMPLE 4 Using the general procedure of Example 1, 5,8-methano-5,8-dihydro 1,4 naphthohydroquinone is prepared by heating at reflux, 5,8-methano-5,8-dihydro-1,4-naphthoquinone, 5 grams, water, 5 grams, and methyl alcohol,

50 grams.

EXAMPLE 5 6 I claim: 1. A process for preparing a methano-polycyclic hydroquinone having the following formulae 1: OH x on R.

l l l x a. x R.

IX X and IX X I x R, x R;

V l x hr: x H 1'1.

wherein X is selected from the group consisting of hydrogen, chlorine and bromine; R and R are independently selected from the group consisting of chlorine, bromine, lower alkyl, lower alkenyl and hydrogen; R R4, R and R are selected from the group consisting of chlorine, bromine and hydrogen which comprises rearranging a corresponding methano-polycyclic quinone under isomerization conditions at a temperature of from about 25 C. to about 200 C. in the presence of a ketone selected from the group consisting of acetone and methyl ethyl ketone or acetonitrile as an inert solvent and water and thereafter recovering the desired hydroquinone product.

2. The process of claim 1 wherein the solvent is present in an amount of from about 0.5 to 15 weight parts per 1 weight part of the quinone.

3. The process of claim 1 wherein the water is present in an amount of from about 0.10 to about 2.0 weight parts per 1 weight part of the quinone.

4. The process of claim 1 wherein 5,6,7,8,9,9-hexachloro-5,8-methano 5,8 dihydro 1,4 naphthohydroquinone is produced by rearranging 5,6,7,8,9,9-hexachloro-5,8-methano-5,8-dihydro-1,4-naphthoquinone.

5. The process of claim 1 wherein the solvent is acetonitrile.

6. The process of claim '1 wherein 5,6,7,8,9,9-hexachloro-5,8-methano 5,8 dihydro 1,4 naphthohydroquinone is prepared by rearranging 5,6,7,8,9,9-hexachloro-5,8-methano-5,8-dihydro-1,4-naphthoquinone at a temperature within the range of from about 25 to about 200 C. in the presence of from about 0.5 to about 15 weight parts of solvent per 1 weight part of the quinone and from about 0.10 to about 2.0 weight parts of water per 1 weight part of the quinone.

7. The process according to claim 6 wherein the temperature is from about 50 to about C.

8. The process according to claim 6 wherein the solvent is present in an amount of from about 2.5 to about 12 weight parts per 1 weight part of the quinone.

9. The process of claim 6 wherein the water is present in an amount of from about 0.20 to about 1.25 weight parts per 1 weight part of the quinone.

'10. The process of claim 6 wherein the solvent is methyl ethyl ketone.

References Cited UNITED STATES PATENTS 2,369,196 2/ 1945 Williams et a1. 260--624E 2,584,140 2/ 1952 Segel et a1. 260-4521 R 3,487,117 12/ 19-69 Altwicker 260-623 R 3,678,116 7/1972 Carlson 260-621 R BERNARD HELFIN, Primary Examiner W. B. LONE, Assistant Examiner US. Cl. X.R. 260-62l R, 623 R, 625

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 5,810,9h5; V Dated May 1n, 197a Arthur W, Carlson Inventor(s) It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

In column 2,. lines 36' to 45 formula I V, l appearing as IV should reaci fqllotgs:

- OH R X X R Ir. column 3, line 23 for anophthoquinones read anonapht'noquinones t In column 1, line 22 for "8," reac": 18,

FORM PO-IOSO (10-69) uscoMM-Dc cove-Pen 0.5. GOVERNMENT IIINTIIIG OFFICE: 9 930 Patent No. 3,810,945 Dated may 14, 1974 flfi Arthur W. Carlson hove-identified patent error appears in the a d as shown below:

It is certified that hereby correcte and that said Letters Patent are In column 1, line 22 for "8, read 18, In column 2 lines 26 to 35 formula III, appearing as III should read as follows:

III

Signed and sealed this 17th day of September 1974.

(SEAL) Attest:

C. MARSHALL DANN McCOY M. GIBSON JR. Attesting Officer Commissioner of Patents 

